Complexes of Group 1 Salts with N,N′ ‐Aromatic Bidentate Ligands, of 1 : 1 Salt : Base Ratio

The present and three subsequent papers describe the syntheses and structural characterization of crystalline adducts, sometimes solvated, obtained from (usually methanolic) solutions of simple group 1 metal salts, MX, with the N,N′ ‐aromatic bases L = 2,2′‐bipyridine (‘bpy’), 1,10‐phenanthroline (‘phen’) and 2,9‐dimethyl,1,10‐phenanthroline (‘dmp’) of 1:n (n = 1,2,3 and some non‐integral) stoichiometries and anhydrous conditions. X are predominantly weakly basic oxyanions ClO 4 , NO 3 , O 3 SCF 3 (= ‘triflate’, ‘tfs’) and (pseudo‐) halides for M = Li, Na, K, Rb ( not , as yet, Cs). The present paper describes adducts of 1:1 (or near 1:1) MX : L stoichiometry. The majority of arrays described are single‐stranded one‐dimensional linear polymers, LM units being bridged by oxyanions: single‐stranded LiNO 3 : dmp (1:1) (∞|∞) , (the Na analogue is isomorphous, but with a different anion bonding mode), and double‐stranded NaClO 4 : bpy (1:1) (∞|∞) and Mtfs : dmp (1:1) (∞|∞) (M = Na, K, Rb); an interesting single‐stranded ‘hydrolysis’ product, with supernumerary interleaving phen moieties ‘solvating’ as well as methanol, is defined as NaI : phen : H 2 O : MeOH (1:1(+1):2:1), [(phen)Na(μ‐ O H 2 ) 2 ] (∞|∞) I·phen·MeOH. The complex LiCl : dmp (2:2) is a dimer, [(dmp)Li(μ‐Cl) 2 Li(dmp)], while the LiBr : dmp system is defined in terms of two ionic adductsLiBr : dmp : MeOH (1:1:2.5) ≡ [(dmp)Li(H O Me) 2 ]Br· 0.5MeOH and LiBr : dmp : MeOH : H 2 O (1:1(+1):1:1), ‘solvated’ with dmp, MeOH and H 2 O, as [(dmp)Li(H O Me)( O H 2 )]Br·dmp; also of this family is LiNCS : dmp : MeOH (1:1:1) ≡ [(dmp)Li( N CS)(H O Me)]. The adduct KPF 6 : dmp (1:1) (∞|∞) is a novel double‐stranded one‐dimensional polymer in which (dmp)K units are bridged by PF 6 counterions. Ktfs : dmp : MeOH (2:2:1) 2 is a complex tetramer in which all species are coordinated, but its rubidium counterpart is an infinite polymer. Of more complex stoichiometry are the adducts KI : dmp : MeOH (6:8:3) ≡ [K 6 I 4 (dmp) 8 ]I 2 ·3MeOH containing a ‘polyiodide’ cation, and Ktfs : dmp (4:3), a double‐stranded, one‐dimensional polymer.